CN110885478B - Preparation method of modified aramid pulp masterbatch - Google Patents
Preparation method of modified aramid pulp masterbatch Download PDFInfo
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- CN110885478B CN110885478B CN201911305612.0A CN201911305612A CN110885478B CN 110885478 B CN110885478 B CN 110885478B CN 201911305612 A CN201911305612 A CN 201911305612A CN 110885478 B CN110885478 B CN 110885478B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to the technical field of rubber processing, in particular to a preparation method of modified aramid pulp masterbatch, which comprises the steps of reasonably mixing aramid pulp with a modifier, a coupling agent, a separant, liquid rubber and solid rubber, carrying out chemical grafting modification on the inert surface of the aramid pulp through the modifier, the coupling agent and certain process steps to enable the aramid pulp to be bonded with matrix materials such as rubber and resin, and then selecting the liquid rubber, the separant and the solid rubber to carry out isolation and pre-dispersion on the modified aramid pulp, wherein the obtained aramid pulp masterbatch has good interface strength and dispersibility, and can improve the crack expansion resistance of the matrix and improve the fatigue performance of a damping material when being used as a reinforcing material.
Description
Technical Field
The invention relates to the technical field of rubber processing, in particular to a preparation method of modified aramid pulp masterbatch.
Background
Aramid Pulp (hereinafter referred to as AP) is a highly fibrillated staple fiber, has the characteristics of Aramid such as high modulus, high strength, high stability, toughness and the like, and in order to exert excellent physicochemical properties of AP, the chemical inertness of the surface of the Aramid Pulp is usually changed by physical or chemical means, so that the Aramid Pulp can be used as a special functional assistant and can be well bonded with a matrix material. In addition, AP also has a special three-dimensional structure and a higher specific surface area, and the microfibrils of the AP can anchor pulp in a matrix material to generate a unique 'accordion effect'; but the micro-fibers are easy to be entangled with each other, and AP is difficult to be uniformly dispersed in the matrix material, so that the application range of the micro-fiber is limited; pre-dispersion treatment of the modified AP is required.
Patents US4514541 and EPA0272459 disclose a process for preparing AP pre-dispersed rubber, which comprises mixing AP and reinforcing filler such as carbon black at a certain ratio, stirring at high speed, adding into organic solution or liquid elastomer, stirring, and granulating.
In order to improve the dispersibility of AP in various matrixes, the patent CN1896369A discloses an AP pretreatment method, which comprises the steps of sequentially utilizing low-surface-energy inorganic isolation powder hollow glass beads and a lubricant phthalate compound to carry out powder isolation and lubrication infiltration on the AP so as to thoroughly isolate micro-fibers of the AP, and the AP has excellent dispersibility in various matrixes.
Patent CN102134394B discloses an AP dispersion and a preparation method thereof, the specific method is that AP is pre-dispersed in a dispersion solvent gasoline or ethyl acetate, stirred to be flocculent, then added with a separant white carbon black or pottery clay, silane or titanate coupling agent in sequence for dispersion and modification, then dissolved in a dispersion carrier coumarone resin or phenolic resin, desolventized and crushed to obtain the AP dispersion.
Patent CN105273208B discloses a preparation method of aramid pulp masterbatch, which is to stir aramid pulp, isolation dispersant and bonding resin in a high-speed mixer to obtain surface-modified aramid pulp; premixing the modified aramid pulp compound and a rubber matrix, extruding by a double screw and granulating. The aramid pulp masterbatch prepared by the method can enable aramid pulp fibers to have better dispersibility and reinforcement performance in rubber.
Although the method improves the dispersion effect of the AP in the matrix material, the AP modification effect is not obvious or not enough, the interface strength with the matrix is not obviously improved, and the method is only suitable for the fields of friction, static sealing and the like and is not suitable for vibration reduction and dynamic sealing. The problem of dispersion of the modified AP in the matrix material is mainly solved, and the inventor finds that the preparation of the modified aramid pulp masterbatch is an effective solving means after analysis.
Disclosure of Invention
The invention provides a preparation method of modified aramid pulp masterbatch aiming at various defects in the prior art, which comprises the steps of reasonably mixing aramid pulp with a modifier, a coupling agent, a separant, liquid rubber and solid rubber, carrying out chemical grafting modification on the inert surface of the aramid pulp through the modifier, the coupling agent and certain process steps to ensure that the aramid pulp can be bonded with matrix materials such as rubber, resin and the like, and then selecting the liquid rubber, the separant and the solid rubber to isolate and pre-disperse the modified aramid pulp, so that the obtained aramid pulp masterbatch has good interface strength and dispersibility, and can improve the crack propagation resistance of the matrix and improve the fatigue performance of a damping material when being used as a reinforcing material.
The specific technical scheme of the invention is as follows:
the inventor firstly provides a modified aramid pulp, which comprises the following main components in parts by weight:
10-20 parts of aramid pulp, 2-4 parts of a modifier and 2-4 parts of a coupling agent;
wherein the modifier is polyisocyanate;
the polyisocyanate is further an isocyanate substance containing two or more isocyanate groups, and can be one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate;
the coupling agent is silane coupling agent, such as one of KH-602, KH-590, KH-580, KH-570, KH-560 and KH-550;
on the basis of obtaining the modified aramid pulp, the inventor further discloses a preparation method of the modified aramid pulp masterbatch, which comprises the following specific steps:
1) uniformly mixing 2-4 parts of modifier with a dispersing solvent with the mass 50-200 times of that of the modifier;
2) stirring and dispersing 10-20 parts of aramid pulp in the modifier dilute solution obtained in the step 1), placing the solution in a closed device, and performing stirring heat treatment for 90-240 min at the temperature of 40-100 ℃;
3) adding 2-4 parts of coupling agent into the mixed solution obtained in the step 2), and then continuously stirring and carrying out heat treatment for 90-240 min at the temperature of 40-100 ℃;
4) carrying out desolventizing treatment on the modified aramid pulp mixed solution obtained in the step 3) by adopting a negative pressure suction filtration or centrifugal drying mode;
5) adding 0-40 parts of separant and 5-40 parts of liquid rubber in advance into an internal mixer, mixing for 1-5 min, adding the modified aramid pulp obtained in the step 4), mixing for 25-45 min, adding 5-30 parts of solid rubber, and mixing for 10-20 min to obtain aramid pulp masterbatch;
the parts mentioned in the above process are all parts by weight;
the separant is calcium carbonate or talcum powder or carbon black or white carbon black;
the dispersing solvent adopted in the step is acetone or alkane solvent;
the liquid rubber is diene liquid rubber or alkene liquid rubber, such as liquid polyisoprene and liquid polyisobutylene;
the solid rubber is one or more of natural rubber, ethylene propylene diene monomer, styrene butadiene rubber or butadiene rubber;
the polyisocyanate modifier selected by the invention is an isocyanate substance containing two or more isocyanate groups, and the two or more isocyanate groups on the molecule of the modifier have different activities due to steric hindrance and the like; under the action of steric hindrance, activity inhibition and the like, the isocyanate group with lower activity on the modifier does not react with the AP and is reserved, so that an active group such as amino or isocyanate group is introduced on the surface of the AP; the subsequent process steps of standing, heat treatment and the like can promote the coupling agent to be used as a bridge, and the modified AP and the matrix material generate chemical bonding or hydrogen bond action, so that the modified AP can be used as a reinforcing material to generate effective bonding with the matrix materials such as rubber, resin and the like;
the inventor considers that the dispersion resistance of the modified AP in the liquid rubber is smaller than that of the solid rubber, so that the AP is added into the liquid rubber to be more uniformly dispersed, then the AP is added into the solid rubber, and the AP is better dispersed in the matrix material by utilizing the mixing of the liquid rubber and the solid rubber.
In addition, other processes of the method can adopt conventional processes, have no higher requirements on equipment and process parameters, and can be better adapted to the existing production processes and equipment.
And the isolating agent is added with the liquid rubber, so that the activated pulp dispersion can be isolated and protected, agglomeration is prevented, the dispersing agent has good dispersibility in the matrix material, and the storage is convenient.
The preparation method of the modified aramid pulp masterbatch provided by the invention can better pre-disperse the modified aramid pulp in the masterbatch, and the obtained modified aramid pulp masterbatch can be used as a special functional additive, and can effectively improve the fatigue life of a matrix material after mixing.
Detailed Description
The present invention is further illustrated below with reference to examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way; the parts in the following examples are parts by weight; the mixing process and the equipment both adopt the prior art, and the inventor does not give details;
example 1
A preparation method of modified aramid pulp masterbatch comprises the following specific steps:
1) uniformly mixing 3 parts of toluene diisocyanate and 500 parts of acetone dispersion solvent;
2) stirring and dispersing 15 parts of aramid pulp in the modifier dilute solution obtained in the step 1), placing the solution in a closed device, and performing stirring heat treatment for 120min at the temperature of 50 ℃;
3) adding 3 parts of KH560 into the mixed solution obtained in the step 2), and continuously stirring and thermally treating for 120min at the temperature of 50 ℃;
4) carrying out desolventizing treatment on the modified aramid pulp mixed solution obtained in the step 3) by adopting a negative pressure suction filtration mode;
5) adding 30 parts of light calcium carbonate and 9 parts of polyisoprene liquid rubber LIR-390 in advance into an internal mixer, mixing for 2min, gradually adding the modified aramid pulp obtained in the step 4), mixing for 35min, finally adding 21 parts of natural rubber No. 1 smoked sheet rubber, and mixing for 12min to obtain aramid pulp master batch.
Example 2
A preparation method of modified aramid pulp masterbatch comprises the following specific steps:
1) uniformly mixing 2 parts of hexamethylene diisocyanate and 300 parts of n-hexane dispersion solvent;
2) stirring and dispersing 12 parts of aramid pulp in the modifier dilute solution obtained in the step 1), placing the solution in a closed device, and performing stirring heat treatment for 150min at the temperature of 65 ℃;
3) adding 3 parts of KH550 into the mixed solution obtained in the step 2), and continuously stirring and thermally treating for 120min at the temperature of 65 ℃;
4) carrying out desolventizing treatment on the modified aramid pulp mixed solution obtained in the step 3) in a centrifugal drying mode;
5) adding 25 parts of white carbon black and 15 parts of polyisoprene liquid rubber LIR-390 in advance into an internal mixer, mixing for 2min, gradually adding the modified aramid pulp obtained in the step 4), mixing for 30min, finally adding 15 parts of natural rubber No. 1 smoked sheet rubber, and mixing for 15min to obtain aramid pulp master batch.
Example 3
A preparation method of modified aramid pulp masterbatch comprises the following specific steps:
1) uniformly mixing 2 parts of toluene diisocyanate and 200 parts of cyclohexane dispersion solvent;
2) stirring and dispersing 15 parts of aramid pulp in the modifier dilute solution obtained in the step 1), placing the solution in a closed device, and stirring and thermally treating the solution for 90min at the temperature of 75 ℃;
3) adding 2.5 parts of KH580 into the mixed solution obtained in the step 2), and continuously stirring and thermally treating for 100min at the temperature of 75 ℃;
4) carrying out desolventizing treatment on the modified aramid pulp mixed solution obtained in the step 3) in a centrifugal drying mode;
5) adding 15 parts of carbon black and 15 parts of polyisoprene liquid rubber LIR-390 in advance into an internal mixer, mixing for 2min, gradually adding the modified aramid pulp obtained in the step 4), mixing for 35min, finally adding 10 parts of natural rubber No. 1 smoked sheet rubber, and mixing for 15min to obtain aramid pulp master batch.
Examples of the experiments
Experiments were performed using the modified aramid pulp masterbatch prepared in example 1.
2.5 parts of modified aramid pulp masterbatch is added into a natural rubber formula (the formula is shown in table 1), and the influence of the modified aramid pulp masterbatch on the fatigue life of the material before and after the addition is researched.
TABLE 1 Experimental examples Natural rubber formulations
| Name of raw material | Specification of raw material model | Mass portion of |
| Natural rubber | First-grade tobacco flake glue | 100 |
| Zinc oxide | The content is more than or equal to 99.7 percent | 5 |
| Stearic acid | Type 800 | 1 |
| Carbon black | N330 | 40 |
| Anti-aging agent | 4010NA | 1.5 |
| Anti-aging agent | TMQ | 1.5 |
| Sulfur | IS60 | 1 |
| Accelerator | CZ | 2.5 |
The preparation process of the natural rubber sample containing the modified aramid pulp masterbatch comprises the following steps:
1) first-stage mixing: adding raw rubber into an internal mixer for internal mixing for 2min, adding a compounding agent except the carbon black and the modified aramid pulp masterbatch for internal mixing for 4min, adding the carbon black and the aramid pulp dispersion for internal mixing for 4min, discharging rubber and discharging sheets. And parking for 24 h.
2) And (3) second-stage mixing: adding sulfur and accelerator into the first-stage glue on an open mill, thinly passing for 10 times, rolling for 3 times, and discharging. And parking for 24 h.
3) And (3) vulcanization molding: and pressing the rubber compound after the placement on a vacuum vulcanizing machine to obtain a test piece.
The preparation process of a blank sample, namely a natural rubber sample without modified aramid pulp masterbatch, is the same as the above.
The fatigue life of the two materials is tested according to GB/T1688-.
Table 2 influence of the addition of the modified aramid pulp masterbatch on the fatigue life of the material
Tests show that the fatigue life of the natural rubber without the modified aramid pulp masterbatch is 20 ten thousand times, and the fatigue life of the natural rubber with the modified aramid pulp masterbatch in 2.5 parts by mass is 33 ten thousand times, which is improved by 65 percent and has obvious effect. Meanwhile, the addition amount of the used modified aramid pulp masterbatch is small, the processing performance of the matrix material is not influenced, and the tearing strength of the material can be improved by more than 20% by adding 2.5 parts of aramid pulp. The service life of related products is prolonged, the maintenance cost can be effectively reduced, and the whole life cycle economy of the products is improved.
Claims (4)
1. A preparation method of modified aramid pulp masterbatch is characterized by comprising the following steps: the method comprises the following specific steps:
1) uniformly mixing 2-4 parts of modifier with a dispersing solvent with the mass 50-200 times of that of the modifier;
2) stirring and dispersing 10-20 parts of aramid pulp in the modifier dilute solution obtained in the step 1), placing the solution in a closed device, and performing stirring heat treatment for 90-240 min at the temperature of 40-100 ℃;
3) adding 2-4 parts of coupling agent into the mixed solution obtained in the step 2), and then continuously stirring and carrying out heat treatment for 90-240 min at the temperature of 40-100 ℃;
4) desolventizing the modified aramid pulp mixed solution obtained in the step 3);
5) adding 0-40 parts of separant and 5-40 parts of liquid rubber in advance into an internal mixer, mixing for 1-5 min, adding the modified aramid pulp obtained in the step 4), mixing for 25-45 min, adding 5-30 parts of solid rubber, and mixing for 10-20 min to obtain aramid pulp masterbatch;
the parts mentioned are parts by weight;
wherein the modifier is polyisocyanate; in particular to one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate;
the separant is calcium carbonate or talcum powder or carbon black or white carbon black, and the using amount of the separant is more than 0 part.
2. The preparation method of the modified aramid pulp masterbatch of claim 1, characterized in that:
the coupling agent is a silane coupling agent.
3. The preparation method of the modified aramid pulp masterbatch of claim 1, characterized in that: the adopted dispersing solvent is acetone or alkane solvent.
4. The preparation method of the modified aramid pulp masterbatch of claim 1, characterized in that:
and 4) performing negative pressure suction filtration or centrifugal drying on the desolventizing agent in the step 4).
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| CN113354879B (en) * | 2021-06-16 | 2023-01-24 | 山东非金属材料研究所 | Vibration damping rubber and preparation method thereof |
| CN113817235B (en) * | 2021-10-12 | 2023-05-05 | 无锡安睿驰科技有限公司 | Structure and manufacturing process of puncture-proof mute tire |
| CN115260621B (en) * | 2022-09-14 | 2023-08-25 | 山东非金属材料研究所 | Fatigue-resistant hydrogenated nitrile rubber for ball cage coupler and preparation method thereof |
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